Novel o-(2-alkyl -4 6-dinitro-phenyl)-o&#39;-(alpha-carbalkoxy-alkyl)-carbonates

ABSTRACT

COMPOUNDS OF THE FORMULA   (2,4-DI(O2N-),6-R&#39;&#39;-PHENYL)-OOC-O-CH(-CH3)-(CH2)N-COO-R   WHEREIN   R IS STRAIGHT OR BRANCHED ALKYL OF 1 TO 12 CARBON ATOMS, R&#39;&#39; IS STRAIGHT OR BRANCHED ALKYL OF 1 TO 8 CARBON ATOMS OR CYCLOHEXYL, AND N IS 0 OR 1;   THE COMPOUNDS ARE USEFUL AS PHYTO-COMPATIBLE ACARICIDES.

United States Patent 3,655,717 NOVEL O-(Z-ALKYL 4,6-DlNITRO-PHENYL} 0-(a-CARBALKOXY-ALKYD-CARBONATES Heinz-Manfred Becher, Bingen (Rhine) and Richard Sehrmg, Ingelheim (Rhine), Germany, assignors to Boehringer Ingelheim G.m.b.H., Ingelheim am Rhine, Germany No Drawing. Filed June 9, 1970, Ser. No. 45,274 Claims priority, application Germany, June 16, 1969, P 19 30 593.2; Dec. 5, 1969, P 19 61 210.3 Int. Cl. C07c 69/68, 69/00; A0ln 9/26 U.S. Cl. 260-463 4 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula o-c-o-cu-(cmM-coon N0 0 CH wherein R is straight or branched alkyl of l to 12 carbon atoms, R is straight or branched alkyl of l to 8 carbon atoms or cyclohexyl, and n is 0 or 1;

the compounds are useful as phyto-compatible acaricides.

This invention relates to novel acan'cidal O-(Z-alkyl- 4,6-dinitro-phenyl)-O'-(a-carbalkoxy-alkyl)-carbonates, as well as to a method of preparing these compounds.

More particularly, the present invention relates to a novel class of compounds represented by the formula N02 0 CH3 wherein R is straight or branched alkyl of 1 to 12 carbon atoms,

R is straight or branched alkyl of 1 to 8 carbon atoms or cyclohexyl, and

n is 0 or 1.

A compound of the Formula I is prepared by either of the following methods:

METHOD A By reacting a 2-alkyl-4,6-dinitro-phenol compound of the formula wherein R has the same meanings as in Formula I, and A is hydrogen or an alkali metal,

with phosgene to form a chlorocarbonate of the formula 9 o-c-cl 3,655,717 Patented Apr. 11, 1972 "ice where R has the same meanings as in Formula I, and reacting the intermediate Ila with a hydroxy-alkanoic acid ester of the formula no-cn-(cn l cooa (III) wherein R and n have the same meanings as in Formula I.

METHOD B II c1- c c ca (0H coon IV(a) Where R and n have the same meanings as in Formula I, and reacting the intermediate IVa with a 2-alkyl-4,6-dinitrophenol of the formula where R has the same meanings as in Formula I.

In either of these methods, the reaction of the starting compound II or IV with phosgene, as well as the subsequent esterification of the intermediate IIa or IVa with the compound III or V, respectively, are preferably car ried out in the presence of an inert organic solvent and in the presence of an acid-binding agent. Examples of suitable organic solvents are aromatic hydrocarbons, such as benzene, toluene or xylene, and ethers, such as tetrahydrofuran or dioxane. Examples of suitable acid-binding agents are alkali metal carbonates, alkali metal bicarbonates, alkali metal oxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkaline earth metal oxides, as well as organic bases, such as triethylamine, pyridine, N,N-dicyclohexyl-ethylamine and the like.

.Also, in either of these methods, it is not necessary to isolate the intermediate chlorocarbonate Ila or IVa from the reaction mixture in which it is formed.

The starting compounds II and IV for methods A and B are known compounds.

The following examples further illustrate the present invention and will enable others skilled in the art to understand it more completely. It should be understood, however, that the invention is not limited solely to the particular examples given below.

EXAMPLE 1 Preparation of O-(2-sec.butyl-4,6-dinitro-phenyl)-O'- (l-ethoxycarbonyl-ethyl-l)-carbonate by method B A solution of 10.0 gm. (0.0416 mol) of 2-sec.butyl- 4,6-dinitro-phenol, 8.8 gm. (0.049 mol) of O-chloroformyl ethyl lactate (prepared by reacting ethyl lactate with phosgene) and 3.5 gm. (0.044 mol) of pyridine in ml. of benzene was stirred at room temperature for several hours. Thereafter, the pyridine hydrochloride which had crystallized out was separated by vacuum filtration. The filtrate was extracted several times with anhydrous potassium carbonate to remove unreacted 2-sec. butyl-4,6-dini- EXAMPLE 2 Using a procedure analogous to that described in Example 1, O- (2-see.butyl-4,6-dinitro-phenyl) -O'-[ l-ethoxycarbonyl-n-'propyl-( 2) ]-carbonate, a yellowish non-crystallizable oil, of the formula CH3 6a x 9 o-c-o-ca-cfi -cooc u o CH3 was prepared from O chloroformyl ethyl-fl-hydroxybutyrate and 2-see.butyl-4,6-dinitro phenol.

Elemental analysis.Calculated (percent): C, 51.3; H, 5.56; N, 7.04. Found (percent): C, 51.2; H, 5.47; N, 7.01.

EXAMPLE 3 Using a procedure analogous to that described in Example 1, 0-(2-sec.butyl-4,6-dinitro-phenyl)-O-[1 methoxy-carbonyl-ethyl] -carbonate, a yellowish non-crystallizable oil, of the formula was prepared from O-chloroformyl methyl lactate and 2- sec. butyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent) C, 48.6; H, 4.89; N, 7.57. Found (percent): C, 48.5; H, 4.77; N, 7.51.

EXAMPLE 4 Using a procedure analogous to that described in Example 1, O (2-sec.butyl-4,6-dinitro-phenyl)-O"-[l-isopropoxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula 0 o E o en cooca(ca N02 CH3 was prepared from O-chloroformyl isopropyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 51.3; H, 5.56; N, 7.04. Found (percent): C, 51.0; H, 5.32; N, 6.89.

EXAMPLE 5 Using a procedure analogous to that described in Example 1, O (2 sec.buty1-4,6-dinitro-phenyl)-O'-[l-nbutoxycarbonyl-ethyl] -carbonate, a yellowish non-crystallizable oil, of the formula CH3 6H C235 9 c o ca OOO-n-Chlig was prepared from O-chloroformyl n-butyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 52.5; H, 5.86; N, 6.80. Found (percent): C, 52.6; H, 5.89; N, 6.95.

EXAMPLE 6 Using a procedure analogous to that described in Example 1, O-(2-sec.butyl-4,6-dinitro-phenyl)-O-[1-namyloxycarbonyl-ethyl] -carbonate, a yellowish non-crystallizable oil, of the formula CH3 0 (in c 11 ll 0 C 0 (3H COO-n-G5H11 2 3. was prepared from O-chloroformyl n-amyl lactate and 2-sec.butyl-4,6-dinitro-phenol Elemental analysis.-Calculated (percent): C, 53.6; H, 6.11; N, 6.58. Found (percent): C, 53.3; H, 5.93; N, 6.71.

EXAMPLE 7 Using a procedure analogous to that described in Example 1, O- 2-sec.butyl-4,6-dinitro-phenyl) -O'- l-isoamyloxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula 2 /CH e 3 0 II o c o ca COO-iBO-C5H11 was prepared from O-chloroformyl isoamyl lactate and 2-sec.butyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 53.6; H, 6.11; N, 6.58. Found (percent): C, 53.4; H, 5.90; N, 6.75.

EXAMPLE 8 Using a procedure analogous to that described in Example 1, 0-(2-sec.butyl-4,6-dinitro-phenyl)-O'-[1-n-octyloxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula 9 02 CH Cgll'g 0 C O 0H COO-n-CaH 2 3 was prepared from O-chloroformyl n-octyl lactate and 2-sec.butyl-4,6-dinitro-phenol,.

Elemental analysis-Calculated (percent): C, 56.5; H, 6.90; N, 5.98. Found (percent): C, 56.2; H, 6.78; N, 6.06.

EXAMPLE 9 Using a procedure analogous to that described in Example 1, 0-(2-sec.butyl-4,6-dinitro-phenyl) O [methoxycarbonyl-n-propyl-(2)]-carbonate, a yellowish noncrystallizable oil, of the formula 9 3 021.; CH Cal-r5 9 0-c-o-eH-ca -cooea Q2 CH3 was prepared from 9.0 gm. of O-chloroformyl methyl fi-hydroxybutyrate and 10.0 gm. of 2-sec.butyl-4,6-dinitro-phenol in the presence of 3.5 gm. of pyridine and 100 ml. tetrahydrofuran. The yield was in excess of of theory.

EXAMPLE 10 Using a procedure analogous to that described in Example 1, O-(2-sec.butyl-4,6-dinitro-phenyl)-0-[l-isoamyloxycarbonyl-n-propyl-(2)] -carbonate, a yellowish non-crystallizable oil, of the formula 9 o c o git c11 coo-1504 11 N02 CH was prepared from 17.5 gm. of O-chloroformyl isoamyl fl-hydroxy-butyrate and 15.0 gm. of 2-sec.-butyl-4,6-dinitro-phenol in the presence of 5.2 gm. of pyridine and 200 ml. of dioxane.

EXAMPLE 11 C O ll-i CH2COO-n-C H 02 CH3 1 was prepared from O-chloroformyl n-dodecyl fl-hydroxybutyrate and 2-sec.butyl-4,6-dinitro-phenol.

EXAMPLE 12 Preparation of O-(2-sec.butyl-4,6-dinitro-phenyl)- O'-( l-ethoxycarb onyl-ethyl) carbonate 24.0 gm. (0.10 mol) of 2-sec.butyl-4,6-dinitro-phenol were dissolved in 100 ml. of acetone, and then 556 gm. (0.0525 mol) of anhydrous sodium carbonate were added to the solution. The resulting mixture was boiled until the sodium carbonate had almost completely gone into solution (for about 30 minutes), and then the still undissolved sodium carbonate was filtered off and the filter cake was Washed with acetone. 19.0 gm. (0.105 mol) of O-chloroformyl ethyl lactate were added to the filtrate, and the resulting solution was refluxed for two hours. Thereafter, the sodium chloride which had separated out was isolated from the solution by centrifuging and vacuum-filtration and washed with acetone. The wash liquid was combined with the filtrate, and the solution was evaporated until an oily residue was left. Finally, the oily residue was heated for 20 minutes at about 100 C. in a high vacuum to remove all residual volatile impurities. 37.7 gm. (98% of theory) of O-(2-sec.butyl-4,6-dinitro phenyl) O' (1 ethoxycarbonyl-ethyl) carbonate were obtained.

EXAMPLE 13 Preparation of O-(2-sec.amyl-4,6-dinitro-phenyl)- O-( l-ethoxycarbonyl-ethyl) carbonate A solution of 12.7 gm. (0.050 mol) of 2-sec.amyl-4,6 dinitro-phenol, 10.8 gm. (0.060 mol) of O-chloroformyl ethyl acetate and 4.7 gm. (0.059 mol) of pyridine in 100 ml. of benzene was stirred for several hours at room temperature. Thereafter the pyridine hydrochloride which had crystallized out was separated by vacuum-filtration, and the filtrate was extracted several times with anhydrous potassium carbonate to remove unreacted 2-sec. amyl-4,6-dinitrophenol. The filtrate was then distilled, initially at atmospheric pressure and toward the end in vacuo, to remove the benzene, leaving 19.1 gm. (96% of theory) of an oily residue which was identified to be 0- (2-sec.amyl-4;6-dinitro-pheny'l) O' (l-ethoxycarbonylethyl)carbonate of the formula a O N cn '-(c1-r CH 0 5 o cu cooc H 2 3 The product was thin-layer chromatographically uniform. Elemental analysis.Calculated (percent): C, 51.3; H,

6 5.56; N, 7.04. Found (percent): C, 51.1; H, 5.77; N, 6.86.

EXAMPLE 14 Using a procedure analogous to that described in Example 13, O-(2-mthyl-4,6-dinitro-pheny1)-O-[l-ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula o-c-o-cH-cooc 1r 02 CH3 was prepared from O-chloroformyl ethyl lactate and 2- methyl-4,6-dinitro-phenol.

Elemental analysis.--Calculated (percent):: C, 45.60; H, 4.12; N, 8.18. Found (percent): C, 45.52; H, 4.25; N, 8.06.

EXAMPLE 15 Using a procedure analogous to that described in Example 13, O-(2-methyl-4,6-dinitro-phenyl)-O'-[l-n-butoxycarbonyl-ethyl]-carbonate, an oil, of the formula c n c11 9 o c o git COO-n-C4I-l' N02 CH3 was prepared from '0-chloroformyl n-butyl lactate and 2-methyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 48.6; H, 4.90; N, 7.57. Found (percent): C, 48.54; H, 4.99; N, 7.51.

EXAMPLE 16 Using a procedure analogous to that described in EX- ample 13, 0- 2-isopropyl-4,G-dinitro-phenyl) -O'- l-ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula c n CH(CH3)2 o 0-C-0-QH-CO0C2H5 o CH was prepared from O-chloroformyl ethyl lactate and 2- isopropyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 48.60; H, 4.90; N, 7.57. Found (percent): C, 48.52; H, 4.84; N, 7.47.

EXAMPLE 17 Using a procedure analogous to that described in Example 13, O-(2-n-butyl-4,6-dinitro-phenyl)-O'-[1-ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula 02M CW9 9 c o en cooc ir N02 CH3 was prepared from O-choroformyl ethyl lactate and 2-nbutyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 50.00; H, 5.24; N, 7.29. Found (percent): C, 49.79; H, 5.32; N, 7.18.

EXAMPLE 18 EXAMPLE 19 Using a procedure analogous to that described in Example 13, O-(2-sec.amyl-4,6 dinitro-phenyl)-O'-[1-ethoxy carbonyl-ethyl]-carbonate, an oil, was prepared from 0- chloroformyl ethyl lactate and 2 sec.amyl-4,6-dinitrophenol.

7 Elemental analysis.Calculated (percent): C, 51.30; H, 5.56; N, 7.04. Found (percent): C, 51.10; H, 5.77; N 6.86.

EXAMPLE 20 Using a procedure analogous to that described in Example 13, O- 2-sec.amyl-4,6-dinitro-phenyl -O'- 1-n-butoxycarbonyl-ethyl]-carbonate, an oil, was prepared from O chlorofrornyl n-butyl lactate and 2-sec.arnyl-4,6-di nitrophenol.

Elemental analysis.-Calculated (percent): C, 53.60; H, 6.15; N, 6.58. Found (percent): C, 53.33; H, 6.20; N, 6.39.

EXAMPLE 21 Using a procedure analogous to that described in Example 13, O (2 sec.amyl-4,6-dinitro-phenyl)-O'-[l-noctyloxycarbonyl-ethyl]-carbonate, an oil, was prepared from O-chloroformyl n-octyl lactate and 2-sec.amyl-4,6- dinitro-phenol.

Elemental analysis-Calculated (percent): C, 57.40; H, 7.11; N, 5.81. Found (percent): C, 57.06; H, 7.24; N, 5.60.

EXAMPLE 22 Using a procedure analogous to that described in Example 13, O (2-sec.amyl-4,6-dinitro-phenyl)-O'-[l-ethoxycarbonyl-n-propyl-(Z)] carbonate, an oil, was pre pared from O-chloroformyl ethyl ;3-hydroxy-butyrate 2- sec.amyl-4,6-dinitro-phenol.

Elemental analysis.--Calculated (percent): C, 52.50; H, 5.85; N, 6.80. Found (percent): C, 52.21; H, 5.98; N, 6.52.

EXAMPLE 23 Using a procedure analogous to that described in Example 13, O (2-sec.octyl-4,6-dinitro-phenyl)-O'-[l-ethoxycarbonyl-ethyl]-carbonate, a yellowish non-crystallizable oil, of the formula 9 H (ca 011 o. o-ii-o-cH-cooc tr 0 6a was prepared from O-chloroformyl ethyl lactate and 2- sec.octyl-4,6-dinitro-phenol.

Elemental analysis.-Calculated (percent): C, 54.50; H, 6.41; N, 6.37. Found (percent): C, 54.27; H, 6.43; N, 6.28.

EXAMPLE 24 Using a procedure analogous to that described in Example 13, O (2 cyclohexyl-4,6-dinitro-phenyl)-0-[1- ethoxycarbonyl-ethyl]-carbonate, an oil, of the formula .o-c-o-gn-gooc n N02 CH3 was prepared from O-chloroformyl ethyl lactate and 2- cyclohexyl-4,6-dinitro-phenol.

Elemental analysis.Calculated (percent): C, 52.70; H, 5.40; N, 6.84. Found (percent): C, 52.44; H, 5.49; N, 6.57.

The compounds according to the present invention, that is, those embraced by Formula I above, have useful properties. More particularly, they all exhibit very eifective acaricidal activities, especially against red spider mites, while being non-toxic toward plants; a few of them also exhibit fungicidal, insecticidal and ovicidal actvities.

For acaricidal purposes the compounds according to the present invention are applied as active ingredients in conventional liquid or solid pesticidal compositions, such as dusting powders, suspensions, emulsions, solutions, aerosols and the like. Such compositions may additionally comprise customary inert auxiliary ingredients, such as emulsifiers, diluents and adhesion-enhancing agents, as well as additional pesticidal agents. The effective acaricidal concentration range of the compounds of the instant invention in such compositions is from 0.001 to 5% by weight, based on the total weight of the composition.

The following examples illustrate a few acaricidal compositions comprising a compound of the present invention as an active ingredient and represent the best modes contemplated of putting the invention into practical use. The .parts are parts by weight unless otherwise specified.

EXAMPLE 25 Emulsion concentrate 20 parts of O-(2-sec.butyl-4,6-dinitro-phenyl)-O-'-(lethoxycarbonyl-ethyl)-carbonate and 10 parts of butyl ricinoleate sulfonate were dissolved in parts of a commercial mixture of aromatic hydrocarbons. The resulting concentrate was then emulsified in the required amount of Water to make the concentration of the mixed carbonate in the aqueous emulsion about 0.02%. The emulsion was then sprayed at the rate of 2,000 liters/hectare on a apple orchard infested with red spider mites. A kill of the spider mites was achieved without injury to the apple trees.

EXAMPLE 26 Wettable powder 20 parts of O-(2-sec.butyl-4,6-dinitro-phenyl)-O-[1- methoxycarbonyl-n-propyl-(2)]-carbonate, 20 parts of kaolin, 5 parts of sodium sulfate, 2 parts of finely divided calcium carbonate, 8 parts of calcium liguin sulfonate, 2 parts of alkyl naphthalene sulfonate and 43 parts of siliceous chalk were intimately admixed with each other, and the mixture was milled. The resulting powder was suspended in a sufiicient amount of water to make the concentration of the mixed carbonate in the aqueous suspension about 0.04%. The suspension was then sprayed at the rate of 2,000 liters/hectare on a apple orchard intested with red spider mites. A 100% kill of the spider mites was obtained without injury to the apple trees.

EXAMPLE 27 Dusting powder 2 parts of O-(2-sec.butyl-4,6-dinitro-phenyl)-O'-( lethoxycarbonyl-ethyl)-carbonate were intimately admixed with 98 parts of kaolin, and the mixture was milled. The resulting powder was dusted at the rate of 30 kg./hectare on a bean field infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the bean plants.

EXAMPLE 28 Wettable powder A mixture of 25 parts of O-(2-sec.amyl-4,6-dinitrophenyl) O (1-ethoxycarbonyl-ethyl)-carbonate and 25 parts of diatomaceous earth was thoroughly milled with 2 parts of prepared chalk (calcium carbonate), 5 parts of anhydrous sodium sulfate, 33 parts of siliceous chalk, 9 parts of a stabilizer (Collex and 1 part of a sodium alkylnaphthalenesulfonate wetting agent (Nekal BX-78, GAF Corp.). The resulting powder was suspended in a sufficient amount of water to make the concentration of the mixed carbonate in the aqueous suspension about 0.03%. The aqueous suspension was sprayed at the rate of 2,000 liters/hectare on a apple orchard infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the apple trees.

EXAMPLE 29 Dusting powder A mixture of 2 parts of O-(2-sec.amyl-4,6-dinitrophenyl) O (1 ethoxycarbonyl-ethyl)-canbonate and 2 parts of diatomaceous earth was thoroughly admixed with 96 parts of kaolin, and the mixture was milled. The resulting powder was dusted at the rate of 20 kg./hectare on a bean field infested with red spider mites. A 100% kill of the spider mites was obtained without injury to the bean plants.

Analogous results were obtained when an equal amount of any one of the other compounds embraced by Formula I was substituted for the particular mixed carbonate in Examples 25 through 29. Likewise, the concentration of the active acaricidal ingredient in these examples may be varied, as may the amounts and nature of the inert ingredients, to meet particular requirements.

While the present invention has been illustrated with the aid of certain specific embodiments thereof, it will be readily apparent to others skilled in the art that the invention is not limited to these particular embodiments, and that various changes and modifications may be made without departing from the spiirt of the invention or the scope of the appended claims.

We claim:

1. A compound of the formula o-g-o-ga-(cu -coon 2 3 wherein R is straight or branched alkyl of 1 to 12 carbon atoms,

'R is straight or branched alkyl of 1 to 8 carbon atoms or cyclohexyl, and n is 0 or 1.

2. A compound according to claim 1, which is O-(2-sec. butyl 4,6 dinitro-phenyl)-O'-(1-ethoxycarbonylethyl)- carbonate.

3. A compound according to claim 1, which is O-(2- sec.butyl 4,6 dinitro-phenyl)-O'-[l-methoxy-carbonyln-propyl- (2) ]-carbonate.

4. A compound according to claim 1, which is 0-(2-sec. amyl 4,6 dinitro-phenyl)-O'-(1-ethoxycarbonylethyl)- carbonate.

References Cited UNITED STATES PATENTS 3,234,260 2/ 1966 Pianka et a1 260463 3,419,620 12/1968 Becker et a1. 260-611 FOREIGN PATENTS 1,550,196 12/1968 France.

LEWIS GO'ITS, Primary Examiner D. G. RIVERS, Assistant Examiner US. Cl. X.R. 424301 P0405 UNITED STATES PATENT OFFICE (5/69) CERTIFICATE OF CORRECTION Patent No. 3,655,717 Dated pri 11, 1972 Inventor) Heinz-Manfred Becher and Richard Sehring It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

1 Column L, line 32, correct the formula to read OQN l CH -OC H I o' ('3'. o qH COO-1so-C H Column 4,-1ine 58, after insert .--1-

Signed and sealed this 21st day of November 1972.

(SEAL) Attest: EDWARD M.FLETCIER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

